ESCHEM101

L E S S O N 3 : E N E R GY

E N G R . PA N G A N I B A N
SOIL
FUELS
Let’s Define!

FUEL - are reduced forms of matter (containing

carbon as a main constituent) that burn readily in the
presence of oxygen

*How can fuel release energy?

COMBUSTION
Combustion is an oxidation reaction that produces large amount of heat
that we may utilized the energy released from the process to be used
economically for domestic and industrial purpose
• Oxidation Reaction – a chemical reaction in which a substance loses one or more
electrons; where a substance (fuel) reacts with oxygen and produces oxides.
• Oxides – a chemical compound that contains at least one oxygen atom and one other
chemical formula (ex. CO2, H2O, NOx)
• Chemical reaction – conversion of reactants into products that requires some chemical
bonds in the reactant be broken
• Hydrocarbons – compounds composed of only carbon and hydrogen, a combustible
fuel source
HYDROCARBONS
SATURATED HYDROCARBONS (ALKANES) HAVE GENERAL
FORMULA CnH2n+2 n NAME CHEMICAL FORMULA
1 methane CH4
2 ethane C2H6
3 propane C3H8
4 butane C4H10
5 pentane
6 hexane
7 heptane
8 octane
9 nonane
10 decane
Combustion of Hydrocarbons
General equation for the combustion of a hydrocarbon:
Fuel + O2 → CO2 + H2O

Fuel value of a substance is the heat released when one gram of the substance is combusted.
Also called as energy or calorific value.

Heat of Combustion – the amount of heat energy released when a fuel is burned
Below are the average bond enthalpies (in kJ/mol) of a number of atom pairs that might be
involved in the combustion of a hydrocarbon or related fuel. The greater the bond enthalpy, the
stronger the bond.
Sample Exercise!
COMBUSTION OF METHANE:
a) Write a balanced Chemical Equation.
b) How much heat is released (heat of combustion) in a complete combustion of
methane?
c) What is the Fuel value of methane?
d) How many moles of O2 are required if 6 mol of CH4 is to be completely
consumed?
e) How many grams of water is produced if enough oxygen gas reacts with 25 g of
methane?
A generalization is that most hydrocarbons release about 40 – 50 kJ/g of energy upon complete
combustion to carbon dioxide and water.
Factors
Factors other than the actual energy content of the fuel play a big role in determining which of
these fuels we use such as (aside from the fact we know it’s intended use):

• Availability
• Ease of transport and storage
• Pollution – producing potential and perceived danger
• Cost
GOOD FUEL should have:
• High calorific value
• Moderate ignition temperature
• Low moisture content
• Low non-combustible matter content
• Low cost and easy availability
• Easy to transport and storage cost should be low
• Products of combustion should not be harmful
• Burn in air without much smoke
• Combustion should be easily controllable
Classification of Fuels
Fuels may broadly be classified in two ways:
1. According to the physical state in which they exist in nature – solid, liquid and gaseous
2. According to the mode of their procurement – natural and manufactured
Solid Fuels
COAL - most abundant fossil fuel, contains hydrocarbon of high molecular weight as
well as compounds containing sulfur, oxygen, or nitrogen

- Energy in coal initially comes from the Sun, and

is the energy from sunlight trapped by dead

plants (organic matter).

2 Main Phases of Coal Formation
1. Peatification
- bacterial activity that creates the peat
2. Coalification
- increasing the temperature and pressure from burial
Classification of Coal
Classification of Coal
1. Peat
➢ a soft, crumb, dark brown substance that is formed from generations of dead
and partially decaying organic matter
➢ must be buried from 4-10 km deep by sediment
2. Lignite or brown coal
➢ brown in color and the lowest quality of coal; the youngest fossil fuel
produced; contains the large amount of compounds other than carbon – such
as sulfur and mercury
➢ It’s high moisture and lower carbon content results in more CO2 emissions
than harder black coals
 Classification of Coal
3. Sub-Bituminous or black lignite
➢ Grey-black or dark brown coal; ranges from hard to soft as it represents an
intermediate stage between lignite and higher quality bituminous coal
➢ Most commonly used, with 30% of coal resources
4. Bituminous coal
➢ Second highest quality of coal and the most abundant type of coal
➢ The high carbon and low moisture contents make it ideal in the production
of steel and cement, as well as in electricity generation and coke
production
 Classification of Coal
5. Anthracite
➢ Black form of coal and the highest quality coal
➢ Very hard, has low moisture content and carbon content nearly 95% w/w
➢ Since so much energy is released when burned, this fuel is exceptional at
heating up quickly and burning very hot; burn longer than wood
➢ Used for space heating as it is one of the cleanest types of coal to burn –
produces less smoke than others
 Classification of solid fuels & its calorific values

Calorific Value
Fuel Nature Composition % Uses
(kcal/kg)

C = 57
H = 06
Highly fibrous light brown in O = 35 Domestic fuel, power
Peat 4000 – 54000
color generation

C = 67
H = 05
O = 26 Manufacture of producer
Lignite Fibrous, brown colored coal 6500 – 7100
gas and steam

C = 77
H = 05
Sub-bituminous Black colored, homogeneous O = 16 Manufacture of gaseous
7000 – 7500
coal smooth mass fuels

C = 83
H = 05
Black, brittle, burns with yellow O = 10 Power generation, coke
Bituminous coal 8000 – 8500
smoky flame making, domestic fuel

C = 93
H = 03
Hard & most matured coal, O = 03 Boiler heating,
Anthracite 8500 – 8700
burns without smoke metallurgical furnace
Solid Fuels
Advantages Disadvantages

✓ Easy to transport ꭓ Contains components that cause air pollution

✓ Convenient to store without any risk ꭓ Calorific value is comparatively low and
thermal efficiency is not so high
of spontaneous explosion
ꭓ Large space storage requirement
✓ Production cost is low
ꭓ Slow combustion process and cannot be
✓ Possess moderate ignition temperature
easily controlled
ꭓ Recovery from its underground deposits is
expensive and often dangerous
Secondary Fuels from Coal
• Syngas or Synthesis Gas, mixture of gaseous hydrocarbons from coal through coal
gasification, a process where coal is pulverized and treated with superheated steam
➢ sulfur-containing compounds, water, and CO2 can be removed from the products leading to
a gaseous mixture of CH4, H2, and CO, all of which have high fuel values.

➢ Combustion of syngas causes less air pollution than burning coal

conversion purification
Coal + steam complex mixture mixture of CH4, H2, CO (syngas)
Secondary Fuels from Coal
• Synthetic Liquid Fuels such as crude oil type, through a process called coal liquefaction
where coal is reacted with hydrogen gas under high pressure in the presence of catalyst
(hydrogenating the coal)
➢ Resulting crude oil product can be fractionally distilled to give fuel oil, gasoline, and certain
hydrocarbons used in the manufacture of plastics, medicines, and other commodities
➢ 5.5 barrels of liquid fuel are produced for each ton of coal yet the cost of barrel of liquid from
coal liquefaction is about double that of a barrel of crude oil
Liquid Fuels
PETROLEUM OR CRUDE OIL - naturally occurring fossil fuel exists in liquid form in
underground reservoirs in the tiny spaces within sedimentary rocks or it can be found near the surface in oil
sands
• It is often found alongside natural gas and saline water
• It gets this nickname as “black gold” from the monumental
number of products that can be processed from unrefined
crude oil
• It is formed as organic-rich rocks are buried and heated
over geological time; resulted from the partial
decomposition of marine animals and vegetables,
organisms and pre-historic forests
• It can either be beneath land or out in the ocean below the
seabed.
 Petroleum Formation

Different combinations of pressure, heat,

Over hundreds and thousands of and the original composition of organic
years, the remains were buried material will determine the type of
Crude oil formed from the remains of hydrocarbon formed (Crude Oil). Some oil
dead organisms (diatoms) such as deeper and deeper under more
might make it all the way to the surface
algae and zooplankton that existed sediment and organic materials. where it pools, in other cases the oil will get
many years ago in marine Enormous pressure, high trapped under impermeable layers of rock
environment. temperatures, and lack of oxygen or clay where it will form underground
transformed the organic matter into a reservoirs.
These organisms absorbed energy waxy substance called kerogen Then Crude oil extraction is drilling through layers
from the sun and stored it as carbon the process called catagenesis of sand, silt, and rock to reach the rock
molecules within their bodies. transforms the kerogen into formations that contain oil and natural gas
hydrocarbons. deposits.
Classification of Petroleum
The chemical nature of crude petroleum varies with the part of the world in which it is found. They
appear, however, to be three principal varieties.
1. Paraffinic Base Type Crude Petroleum, mainly composed of saturated hydrocarbons from CH4
to C35H72 and a little of naphthalene and aromatics. Hydrocarbons from C18H38 to C35H72 are called
waxes
2. Asphaltic Base Type Crude Petroleum, contains aromatic hydrocarbons and cycloparaffins or
naphthalene with small amount of paraffins
3. Mixed Base Type Crude Petroleum, contains both paraffinic and asphaltic hydrocarbons and are
generally rich in semi-solid waxes
 Hydrocarbon Fractions from Petroleum
Fraction Size Range of Molecules Boiling Point Range (°C) Uses
Uncondensed Gases C1 - C4 Below 30 Gas fuels (e.g. LPG)
Petroleum ether C5 – C7 30 – 70 Solvent
Gasoline or petrol C5 – C9 40 – 120 Fuel for IC engines
Straight-run gasoline C5 – C12 30 – 200 Motor fuel
Naphtha or Solvent Spirit C9 – C10 120 – 180 Paints and in dry cleaning
Fuel for stoves and jet
Kerosene oil C10 – C16 180 – 250 engines
Diesel oil C15 – C18 250 – 320 Diesel engine fuel
Lubricating oil, cracking
Lubricants C18 – C20 Over 350 stock

Ships fuel and for

Heavy oil C17 – C30 320 – 400 production of gasoline by
cracking
Paraffin wax C20 – C40 Low melting solids Candles, wax paper
Asphalt Above C40 Gummy residues Road asphalt, roofing tar
Manufactured Liquid Fuels
1. Gasoline or Petrol, obtained either from distillation of crude oil or by
synthesis; it contains some undesirable unsaturated straight chain hydrocarbons
and sulfur compounds.
Characteristics of an ideal gasoline:
➢ It must burn clean and produce no corrosion, etc. on combustion
➢ It should mix readily with air and afford uniform manifold distribution
➢ It must be knock resistant
➢ It should be pre-ignite easily
➢ It must have a high calorific value
Manufactured Liquid Fuels
Octane Number or Octane Rating, the percentage of iso-octane present
in a mixture of iso-octane and n-heptane

Note: The higher the octane number, the better is its performance and
lower knocking properties of gasoline.
Also, octane number does not measure the energy content of the fuel.
Manufactured Liquid Fuels
► Octane rating can be increased either by increasing the percentage of branched-chain and
aromatic hydrocarbon fractions or by adding octane enhancers or increase fraction of octane but
what is important is the compressibility of the gas, not the amount of octane present.
Fuel additives in gasoline:
• Tetraethyl lead – substantially increases compressibility but lead is toxic and ultimately emitted
into the atmosphere and settled into soil and water
• Ethanol – increases oxygen content of gasoline, helps to ensure more complete combustion
and reduces CO2 emissions, hydrocarbons and soot [reformulated gasoline, RFG]
• MTBE (methyl tert-butyl ether, (CH3)3COCH3 – increases octane number and oxygen content of
gasoline; 15% MTBE supplemented to any modern engine but possible carcinogen
Manufactured Liquid Fuels
2. Diesel Fuel, or gas oil. This oil generally contains 85% C and 12% H. Its calorific value is
about 11,000 kcal/kg
➢ Consists of longer hydrocarbons and have low values of ash, sediment, water and
sulphate contents
➢ Easily ignite below compression temperature

Cetane number or Cetane Rating, percentage of cetane (C16H34) present in a mixture of ɑ-methyl
naphthalene and cetane; expresses knocking characteristics of diesel

Note: Oil of high octane number has a low cetane number (vice-versa)
► Cetane number can be increased by adding additive called dopes (ethylnitrate, isoamyl nitrate)
Manufactured Liquid Fuels
3. Kerosene Oil, is used as an illuminant, jet engine fuel, tractor fuel, and
for preparing laboratory gas. By using fair excess of air, it burns with a
smokeless blue flame
4. Heavy Oil, this oil on refractionation gives:
➢ Lubricating oils [and greases]
➢ Petroleum jelly, used as lubricants in medicine and cosmetics
➢ Paraffin wax; used in candles, boot polishes, and electrical
insulations (etc.)
 Liquid Fuels
Advantages Disadvantages
✓ Possess higher calorific value per unit mass than solidꭓ Releases unpleasant odor during incomplete combustion
fuels
ꭓ Some amount of liquid fuels will escape due to evaporation
✓ Burn without dust, ash, clinkers during storage
✓ Easy to transport through pipes ꭓ Specific type of burners required for effective combustion
✓ Require comparatively less storage space ꭓ More expensive than solid fuels
✓ Clean in use and economic to handle ꭓ Costly special storage tanks required for storing liquid fuels
✓ Combustion is uniform and easily controllable ꭓ Greater risk of hazards, particularly in case of highly
inflammable and volatile liquid fuels
✓ Furnace space requirement is lesser than solid fuels
ꭓ Oil can pollute water extensively. Just 1 L of oil can
✓ Requires less excess air for complete combustion
contaminate 1 million L of water.
Gaseous Fuels
- Gaseous fuels occur in nature, besides being manufactured from solid and liquid fuels.

Types of Gaseous Fuel

1. Natural Gas, also called Marsh gas, found in oil fields and coal fields (fire damp); mixture of gases
trapped with petroleum in Earth’s crust and is recoverable from oil wells where gases have migrated
through the rock;
- calorific values from 8,000 to 14,000 kcal/m3
• Lean or Dry Gas, lower hydrocarbons like methane and ethane
• Rich or Wet Gas, higher hydrocarbons like propane, butane along with methane
Uses of Natural Gas:
➢ used as raw material for the manufacturing of carbon black, methane, hydrogen and formaldehyde
➢ excellent domestic fuel and industrial fuel
Types of Gaseous Fuels
2. Synthesis Gas, these gases are chemically made by some process
a. Producer Gas, composed of CO, H2, CO2 and typically a range of hydrocarbons such as
CH4 with nitrogen from the air;
►It has a low calorific value (CV) 1300 to 1800 kcal/m3
▪ It is prepared by passing air mixed with little steam (about 0.35 kg/kg of coal) over a red-hot coal or
coke bed maintained at about 1100OC in a special reactor
▪ Nitrogen in the air remains unchanged and dilutes the gas
▪ Ave. composition:
CO = 22.3%; H2 = 8.12%, N2 = 52.55%,CO2 = 3%
Uses of Producer Gas:
➢ For heating open-hearth furnaces (in steel and glass manufacture), muffle furnaces, retorts (used in
coke and coal gas manufacture)
➢ As reducing agent in metallurgical operations
Types of Gaseous Fuels
b. Blue Gas or Water Gas, consists mainly of CO and H2 with a little fraction of non-
combustible gases; and is produced from syngas
▪ production of a higher calorific value (CV) by intermittently blasting the incandescent bed with air
and steam such the overall heat balance is maintained
▪ Nitrogen gas are discharged to atmosphere and products of the steam blast are kept since they
have higher CV [CV is virtually doubled in this way]
▪ CV is about 2,800 kcal/m3
▪ Ave. composition: H2 = 51%; CO = 41%; N2 = 4%; CO2 = 4%
Carbureted water gas – produced to enhance the energy value of water gas, which is
ordinarily lower than that of coal gas; result of combing the water gas and oil gas methods
▪ Oil is sprayed into the hot water gas chamber to result in a good quality gas
Types of Gaseous Fuels
Uses of Water Gas:
➢ Removal of CO2 from fuel cells
➢ Reacted with producer gas to make fuel gas
➢ Used in the Fisher-Tropsch process
➢ Used to obtain pure hydrogen to synthesize ammonia
➢ Carbureted water gas is used for lighting
 Types of Gaseous Fuels
C. Blast Furnace Gas, a byproduct gas produced during the production of hot metal (liquid iron) in a blast furnace, where
iron ore is reduced with coke to produce hot metal; CV about 1,000 kcal/m3
▪ BFG comes out from the top of the blast furnace is at a high pressure (1.5 to 2.5 atm in modern) and normally at a
temperature of around 100OC to 150OC
▪ Ave. composition:
H2 = 1 to 7%; N2 = 40 to 60%; CO2 = 17 to 25%; CO = 20 to 28%

▪ BFG is a toxic gas, hence, BFG in the environment is measured through CO gas monitor (CO gas concentration must kept
within 50 ppm in the area)
▪ BFG contains much dust and is usually cleaned before use by dust settlers, cyclones or electrolytic precipitators
Uses of Blast Furnace Gas:
➢ In integrated steel plants, BFG is being used mixed with either coke oven gas or converter gas or both; mixed gas is used
as fuel in various furnaces
➢ Can be used in stoves, soaking pits, normalizing and annealing furnaces, foundry core ovens
➢ gas engines for blowing, boilers for power generation, gas turbines for power generation
➢ Used in the sinter plant furnace
Types of Gaseous Fuels
d. Coal and Coke Oven Gas, obtained when it is carbonized or heated in absence of air at
about 1300OC in either coke ovens or gas-making retorts;
► CV about 4,900 kcal/m3
▪ A colorless gas having a characteristic odor; lighter than air and burns with a long smoke flame
▪ Ave. composition: H2 = 47%; CH4 = 32%; CO = 7%; C2H2 = 2%, C2H4
= 3%; N2 = 4%; CO2 = 1%
Uses of Coal Gas:
➢ Used as illuminant in cities and town
➢ Used as fuel and in metallurgical operations for providing reducing atmosphere
 Gaseous Fuels
Advantages Disadvantages
✓ Easier transportation due distribution of fuel throughꭓ Highly inflammable and the chances for fire hazards
pipelines (eliminating manual labor in are extremely high
transportation)
ꭓ Gas occupy large value thus require large storage
✓ It can be lighted at ease tanks
✓ It can be pre-heated by the heat of hot waste gases,ꭓ Very large storage tanks are needed
thereby affecting economy in heat
✓ Combustion can be readily controlled for change in
demand like oxidizing or reducing atmosphere,
length flame, temperature, etc.
✓ Less or negligible ash content and smokeless and
very clean to operate
✓ Gases are miscible with air and hence the excess
air needed is very less
✓ Free from impurities found in solid and liquid fuels
✓ Do not require any special burner technology
End of Lesson 3.2
Lab Activity #3
Energy Content of The Fuels
MATERIALS
• 1 Large Aluminum hollow can (no lid and no bottom)
• 1 small can (or empty aluminum soda can)
• Aluminum foil
• Wooden dowel
• Aluminum foil pan
• 2 lamps containing an assigned fuel (1 for butane and 1 for ethanol/ethyl-alcohol)
• 1 candle
• 1 (3” x 5”) index card (or any sturdy paper)
• 1 immersion thermometer
• Tap Water
• Waste cotton or clean rags
• Fuel (ethanol, butane, candle)